茂金属及后过渡金属均相烯烃聚合催化剂的研究
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摘要
本文设计合成了多个系列的茂金属化合物,研究了它们对α筛烃以及极性烯烃甲基丙烯酸甲酯聚合的催化活性,为开发新型聚合催化剂奠定基础。
首先通过氧桥单茂钛化合物(CPTiCl2)2O (1)与双桥连二环戊二烯基负离子反应,合成了一个新的双桥连双茂(μ-氧)双核钛配合物。将其与氢卤酸反应,以期望断裂氧桥得到顺式双茂型化合物,结果意外的得到了茂环解离产物。所有化合物均被详细表征,并对茂环解离的原因进行了探讨。随后用MAO作为助催化剂详细研究了该系列化合物催化乙烯及苯乙烯的聚合,发现该系列化合物对乙烯催化活性相近,催化剂结构对活性影响较小但对聚合物性质有较大影响。化合物1对苯乙烯聚合的催化活性远远高出其它催化剂,且所得聚合物为等规聚苯乙烯。详细研究了温度、时间、Al/Ti摩尔比等因素对聚合反应的影响,为双金属协同效应提供了一个较好的例证。
对本组以往所报道的二茚铁类化合物与苯炔的Diels-Alder反应进行了扩展,研究了茚基钉及芴基钌化合物与苯炔的Diels-Alder反应,得到了相应的单苯炔及双苯炔加成产物,发现由于热稳定性的关系,钌类化合物的反应性比相应的铁化合物高。在芴基钌化合物与苯炔的反应中意外的得到副产物二苯基芴,尝试用芴基钌化合物与四氯苯炔的反应来解释其反应历程。用X-射线衍射测定了芴基钌化合物苯炔加成产物的分子结构。最后初步尝试了典型化合物在Grubbs催化剂催化下的开环易位聚合反应(ROMP),但没有成功。
首次报道了二茚铁作为中性单组分催化剂催化极性单体甲基丙烯酸甲酯(MMA)和苯乙烯的聚合,详细考察了温度、溶剂以及加入助催化剂对聚合反应的影响,发现提高温度能够大大加快聚合反应速率及单体转化率,溶剂极性以及助催化剂对反应有很大的影响,并对该聚合反应的机理进行了初步探讨,研究了加入自由基阻聚剂对苯醌和TEMPO的聚合反应,发现在自由基阻聚剂的存在下聚合仍然能够进行,否定了该聚合反应的自由基机理,尝试提出了一个可能的机理,即配位聚合机理,并将该聚合反应扩展到茚基铁、茚基钌、芴基钌类似物上。
In this dissertation, several series of metallocene catalysts were designed and synthesized, and their polymerization behaviors of a-olefins and polar monomers were also studied, which could be a basis for developing new types of catalysts for olefin polymerization.
A new doubly bridged bis(cyclopentadienyl) dinuclear (μ-oxo)titanium complex was desiged to be synthesized by the reaction of the lithium compound of the doubly bridged bis(cyclopentadienyl) ligand with the (μ-oxo)semitetallocene titanium complex 1 ([CpTiCl2]2O). Treatment of the compound with concentrated HCl or HBr gave the corresponding Cp-decoordinated products, instead of the expected cis dinuclear metallocene complexes. All these titanium complexes were fully characterized. Their catalytic properties for ethylene and styrene polymerization were also studies in the presence of MAO. The results indicated that these complexes had similar activities for ethylene polymerization and the structures of catalysts had a little effect on catalystic activity but great effects on the properties of the polymers. Compound 1 showed a much higher activity towards styrene polymerization than the others, and the produced polymer is isotactic polystyrene. The influences of temperature, time, Al/Ti ratio were studied in details, which provided a good example for cooperative effects of bimetallic complexes.
To extend the Diels-Alder reaction of benzyne with indenyl iron which reported by our group before the reactions of indenyl and fluorenyl ruthenium complexes with benzyne were studied and the corresponding monoadducts or bisadducts were obtained. Reaction of fluorenyl ruthenium compound with benzyne gave the monoadduct and a byproduct,9,9'-dipehenylfluorene. The possible mechanism of the formation of the byproduct was also studied. Typical complex was also tested for ring-opening metathesis polymerization (ROMP) in the presence of Grubbs' second generation catalyst [(H2IMes)(PCy3)RuCl2=CHPh] but was found to be inactive under normal conditions.
Bis(indenyl)iron as a neutral single-component catalyst methyl methacrylate (MMA) and styrene polymerization was found and the influence of temperature, solvent and cocatalysts were studied in details. A preliminary investigation of the mechanism of the polymerization was carried out. A radical mechanism was denied and a possible mechanism was propesed. In order to extent the application scope of the polymerization, research on the indenyl iron, indenyl nickel and fluorenyl rutheniym complexes were also conducted.
首先通过氧桥单茂钛化合物(CPTiCl2)2O (1)与双桥连二环戊二烯基负离子反应,合成了一个新的双桥连双茂(μ-氧)双核钛配合物。将其与氢卤酸反应,以期望断裂氧桥得到顺式双茂型化合物,结果意外的得到了茂环解离产物。所有化合物均被详细表征,并对茂环解离的原因进行了探讨。随后用MAO作为助催化剂详细研究了该系列化合物催化乙烯及苯乙烯的聚合,发现该系列化合物对乙烯催化活性相近,催化剂结构对活性影响较小但对聚合物性质有较大影响。化合物1对苯乙烯聚合的催化活性远远高出其它催化剂,且所得聚合物为等规聚苯乙烯。详细研究了温度、时间、Al/Ti摩尔比等因素对聚合反应的影响,为双金属协同效应提供了一个较好的例证。
对本组以往所报道的二茚铁类化合物与苯炔的Diels-Alder反应进行了扩展,研究了茚基钉及芴基钌化合物与苯炔的Diels-Alder反应,得到了相应的单苯炔及双苯炔加成产物,发现由于热稳定性的关系,钌类化合物的反应性比相应的铁化合物高。在芴基钌化合物与苯炔的反应中意外的得到副产物二苯基芴,尝试用芴基钌化合物与四氯苯炔的反应来解释其反应历程。用X-射线衍射测定了芴基钌化合物苯炔加成产物的分子结构。最后初步尝试了典型化合物在Grubbs催化剂催化下的开环易位聚合反应(ROMP),但没有成功。
首次报道了二茚铁作为中性单组分催化剂催化极性单体甲基丙烯酸甲酯(MMA)和苯乙烯的聚合,详细考察了温度、溶剂以及加入助催化剂对聚合反应的影响,发现提高温度能够大大加快聚合反应速率及单体转化率,溶剂极性以及助催化剂对反应有很大的影响,并对该聚合反应的机理进行了初步探讨,研究了加入自由基阻聚剂对苯醌和TEMPO的聚合反应,发现在自由基阻聚剂的存在下聚合仍然能够进行,否定了该聚合反应的自由基机理,尝试提出了一个可能的机理,即配位聚合机理,并将该聚合反应扩展到茚基铁、茚基钌、芴基钌类似物上。
In this dissertation, several series of metallocene catalysts were designed and synthesized, and their polymerization behaviors of a-olefins and polar monomers were also studied, which could be a basis for developing new types of catalysts for olefin polymerization.
A new doubly bridged bis(cyclopentadienyl) dinuclear (μ-oxo)titanium complex was desiged to be synthesized by the reaction of the lithium compound of the doubly bridged bis(cyclopentadienyl) ligand with the (μ-oxo)semitetallocene titanium complex 1 ([CpTiCl2]2O). Treatment of the compound with concentrated HCl or HBr gave the corresponding Cp-decoordinated products, instead of the expected cis dinuclear metallocene complexes. All these titanium complexes were fully characterized. Their catalytic properties for ethylene and styrene polymerization were also studies in the presence of MAO. The results indicated that these complexes had similar activities for ethylene polymerization and the structures of catalysts had a little effect on catalystic activity but great effects on the properties of the polymers. Compound 1 showed a much higher activity towards styrene polymerization than the others, and the produced polymer is isotactic polystyrene. The influences of temperature, time, Al/Ti ratio were studied in details, which provided a good example for cooperative effects of bimetallic complexes.
To extend the Diels-Alder reaction of benzyne with indenyl iron which reported by our group before the reactions of indenyl and fluorenyl ruthenium complexes with benzyne were studied and the corresponding monoadducts or bisadducts were obtained. Reaction of fluorenyl ruthenium compound with benzyne gave the monoadduct and a byproduct,9,9'-dipehenylfluorene. The possible mechanism of the formation of the byproduct was also studied. Typical complex was also tested for ring-opening metathesis polymerization (ROMP) in the presence of Grubbs' second generation catalyst [(H2IMes)(PCy3)RuCl2=CHPh] but was found to be inactive under normal conditions.
Bis(indenyl)iron as a neutral single-component catalyst methyl methacrylate (MMA) and styrene polymerization was found and the influence of temperature, solvent and cocatalysts were studied in details. A preliminary investigation of the mechanism of the polymerization was carried out. A radical mechanism was denied and a possible mechanism was propesed. In order to extent the application scope of the polymerization, research on the indenyl iron, indenyl nickel and fluorenyl rutheniym complexes were also conducted.
引文
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[5]程彬,雒雄雄,徐善生,王佰全*二茚铁催化甲基丙烯酸甲酯的链转移聚合,第二十六届中国化学年会会议论文
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